P-acyloxystyrenes and intermediates therefor



UNITED STATES PATENT OFFICE P-ACYLOXYSTYRENES AND INTER- MEDIATES THEREFOR Charles G. overberger, Brooklyn, N. Y., assignor to L. A. Dreyfus Company, Oak Tree, N. J., a company of New York No Drawing. Application December 13, 1949, Serial No. 132,803

3 Claims. (01. 260 .410.5) 1

This invention relates to p-acyloxystyrenes acid. Any acylation step may be used in combihaving unique properties, to intermediates for nation with any desired decarboxylation step. making such p-acyloxystyrenes, and to methods The present invention therefore utilizes a comof making the styrenes, and the intermediates, bination of steps in which p-hydroxycinnamic and their utilization. I

In the prior art, p-acetoxystyrene has been which is then decarboxylated to the correspondproduced by dehydroacetylation of the diacetate ing p-acyloxystyrene. of p-hydroxyphenyl methyl carbinol and the com- The 'p-hydroxycinnamic acid may be obtained pound has also been prepared by the dehydration from any desired source. Th symmetrical trans of p-(a-hydroxyethyl)-phenyl acetate. Higher form is generally obtained in reactions and is acyl derivatives have not been described in the preferably used to the cisisomer. One method literature nor have their properties been disof makin it involves heating benzaldehyde, acetic closed. The methods which have been used are anhydride and sodium acetate to produce connot so desirable for industrial use due to reladensation whereby p-hydroxycinnamic acid (coutively low yields and presence of impurities that maric acid) i obtained. A very satisfactory proafieot the utilization of such materials particucedure involves reaction of p-hydroxy or plarly in the production of polymers and copolyalkoxy benzaldehyde with malonic acid using a mere solvent such as pyridin and a catalyst such as ani- Among the objects of the present invention is line, piperidine, or a tertiary amine. Other solthe production of p-acyloxystyrenes and intervents such as alcohol and other amines, primary mediates therefor giving substantial yields of high and secondary, and ammonia may b used. As

grade products. an example the following is given:

Other objects include the production of such 123 g. (1 mole) of p-hydroxybenzaldehyde and products exhibiting unique properties. 1.04 g. (1 mole) of malonic acid were dissolved in Still further objects include methods of mak- 158.5 (2 moles) of pyridine with aniline as cataing such products and intermediates. lyst and the reaction carried out by heating to a Yet further objects and advantages of the prestemperature of about 60-100" for 3-8 hours. The ent invention will appear from the more detailed product was recrystallized. However p-hydroxydescription set forth below, it being understood cinnamic acid from any source may be used. that this more detailed description is given by The acylation may be carried out using any of way of illustration and explanation only, and not the methods set forth above. The fatty acid by way of limitation, since various changes there chloride will be used illustratively. As exemplary in may be made by those skilled in the art withof such acid halides any fatty acid may be used out departing from the scope and spirit of the having from 3 to 18 carbon atoms and higher.- present invention. As exemplary of such acid halides there may In accordance with the present invention, pbe mentioned propionyl chloride,lauric acid chloacyloxystyrenes are produced by decarboxylaride, palmitic acid chloride, stearic acid chloride,

tlon of p-acyloxyoinnamic acids since it has been etc., so that saturated fatty acid halides are prefound that such cinnamic acid derivatives may ferred. Various methods of acylation may be embe heat treated to remove the carboxyl group 40 ployed. A satisfactory procedure is as follows: leaving the remainder of the molecule intact, the the appropriate acid chloride is added slowly to p-acyloxystyrenes being produced in substantial a cooled solution (5 C. but it may be from 10 yields. The p-acy oxy namic acids are readto 20 C.) of p-hydroxycinnamic acid in a solily produced in substantial yield by acylation of vent such as dry pyridine, and desirably agitated p-hydroxycinnamic acid. The acyl group in the for example for 4 hours at .room temperature. compounds referred to above is desirably a fatty Thedesired product is obtained by acidifying the acid group having at least three carbon atoms, reaction mixture with dilute acid such as sulwhich acyl group is desirably introduced into the phuric acid, desirably cooled, i. e. containing ice,

desired derivatives by the use of the correspondwhereupon the desired product is precipitated. ing acid halide such as chloride or bromide, or In lieu of pyridine, other acid retaining agents acid anhydride. The acylation may also be carmay be employed including alkalis, ammonia,

ried out by ester interchang with an ester of amines, etc. Non-aqueous reaction media are acetic acid catalyzed by acid. It may also be preferably utilized although the reaction may be carried out by treating the appropriate acid chlocarried out in aqueous media with alkalis for ride with the sodium salt of p-hydroxy cinnamic example, but maximum yields are obtained in an 3 indifierent solvent under anhydrous conditions. librium area, as in a crystal solid, but also are In lieu of pyridine, quinoline, other tertiary able to rotat freely about a given axis without amines may be used, such as a-picoline, -picodisturbing the crystalline state by moving the line, 2,6 butadiene, 2,4 butadiene, 2,4,6 collidine, lattice linkages. and other alkyl pyridines; 2-methylquinoline and 5 The transition of such compounds from the i-methylquinoline and other alkyl quinolines. solid to liquidstate takes place in two or more Enough base should be used to adequately remove stages; The. .sm'ectic and nematic phases :reprethe acid formed in the reaction. However, addisent two of a number of geometrically possible tional base is not harmful and is often employed.v intermediate phases. In the smectic state the The temperatures used may be varied, particulo lateral attractions between molecules ar not larly dependent on the acyl ch1orides,-etc. used" broken down. h y are a r n w h h r axe In later stages of reaction, the mixture may-be paralleland are restricted in their movement to heated to moderate temperatures .-to .complete.re-- motion ina series of equispaoed p 8 Sheets, action if necessary. within each of which; however, there is no plan- The p-acyloxycinnamic acids separate as semi- 15 arity of arrangement .and the molecules are free solids or oils and may be purified by recrystallizato move at random. tion as for example from binarymixtures-ofzsol ir In addition 130 the-asymmetry Of molecule, vents such as alcohol-water mixtures. Pe'trothe simultaneous existence of strong dipoles and leum ether (hexane) and benzene may be. used-.1 easily: polarized groups appears to be essential. but offer no advantage. A liquid crystal may be considered a structure of Asgeneralconsideration of theproperties of molecular aggregate resulting. fromlflthenattrac these .p-acyloxycinnamic acids is desirable. Some tion of a dipole-of. one molecule forthereadily.

of them suchas p-caproxy and p-capryloxy cinpolarizable parts of..another. molecule. which in. namicacids do not form. crystals easilyi In.- turn attracts athird moleculeand so on untilfa creasingthe. length of the ester group seems to bundle-like structure is formed.

decrease. the tendency. toward crystallinity. Tha formation. of liquid vcrystals by the p- While the p-acetoxy-cinnamicacid. melts at butyroxy; p-caproxy and p-capryloxycinnamic 206. 0.. to a .clear liquid, thehigher derivatives acids is in accordance withltheabove views; The showv anomalous behavior. For example, p-butymolecules are asymmetrical and 'rectilihear,- withroxy,;p-.caproxy, and p-capryloxycinnamic acids a small degree of internal .iree rotation. The contract between 10V to. 20 below the melting acyloxy group furnishes the. necessary dipole atpoint. and show anomalies on melting due to the traction. p-Acetoxycinnamic acid-forms but one formation-of liqu ystals. Such compou ds liquid :phase; the. lions-occurrence of. a :second preserve apseudocrystallinestructure above the phase is probably due to .the absence of the melting. point which is stable as a cloudy melt methylenicgroup.

between this, temperature and that at which a There is tabulated belowin Table'I exemplary. clearisotropic liquidfis formed. Liquid crystal p-acyloxy-cinnamic acid nd om .of thei1-.. formation is. most: likely to befoundin substances properties:

TABLE I..P-ACYLOXYCINNAMIC 'AGIDS- ii n-c-o--cn=cn-coon 1 1 Per'centGarbon gg Neut:'equiv."= n v g f g Re'cryst. Solvent M. P. Calcd. Found Oalcd. Found Oalcd. some.

0H3; 38 64.07 64.15 4.89. 5.09 206 205.79 ems 70 :44 -65.-21 5.50 5.76 i 220 22o 0111s.; e4 }es.-e5- 66.9! 6.03 5.24 234'- 232* 05m," 85 oo 1751 H7716 }es.es 68.72 15.92. 6.95 2627 260 01H; 78 .do }7o.32.: 70.42 7.64". 7.es.'.-- 290: 289: CnHaa 8s 1:1Benzene-B/Iethanol- }72.s4 72.45 3.13 ass- 346* 346- 015ml 90 3:1'Benzene-Methan0ll} 74.40 74.11 e49 I 9.54 ,4022 402 I 1 Yield of purified product.

3 Yield after one recrystallization. I

3 All melting points are corrected. The first melting point indlcates'the formation oithe cloudy melt (liquid crystal); the second, the formation of clear liquid.

of this characterconsisting of molecules of un- The following examples illustrate" the pro'ducsymmetrical shape, and. particularly in substances tion of these 'p-acylo'xycinnamiciacids,using the in which very long molecules occur. particular reaction conditions set fdrth herein two liquid p e crystalline liquid 65 above,- namely reaction-of-acid chloridewithp andthev amorphous liquid; differ in the degree of hydroxy cinnamic' acid' in a cooledsolutiom (5 O tation- 0f t eir molecular groupings. T e C.-)" in pyridine as solvent,the tin1e-of"reaction*-* former:.'.phase.-;may beregarded as intermediate and-*temperature d recovery being, threbetweena crystalline'solidand a liquid since its set forth. individualparticles are'more .restricted in their movement than those of the liquid and less than Lflp'lsmymxy :cmnamzc aczd those ofithe solid. This situation is clarified by 0.3 molecof 'n-butyryl. ichloride"wereareaoted a consideration of .the.crystal lattice of a long with 9.155 moleof p-hydroxy'cinnamicacidiin.

chain aliphaticcompound, in which the lattice 2.22 moles .ofdry pyridine :under: conditions..set.-..- units are movable not only within a given equiforth-above... Awhiteamorphous.precipitate was.z

II.-p-Caproa:y cinnamic acid 0.3 mole of caproyl chloride was reacted with 0.155 mole of p-hydroxycinnamic acid in dry pyridine solution (2.22 moles) as set forth above. Addition to dilute sulphuric acid (1.153 sp. gr.), gave a yellow oil which formed an amorphous solid within one hour. Recrystallization from alcohol and water with charcoal gave an 85% yield of white crystalline solid having the characteristics set forth in Table I.

Recrystallization of the product from alcohol yielded a small amount of white crystalline material, which on analysis was indicated to be the byproduct of esterification of p-caproxy cinnamic acid by p-hydroxy cinnamic acid.

Analysis calculated for C24H240s2 C, 70.57; H, 5.92. Found: C, 70.54; H, 5.85.

III.p-C'apryloxy cinnamic I acid IV.p-Propiono:cy cinnamic acid 0.22 mole of p-hydroxy'cinnamic acid was reacted with 0.443 mole of propionic acid chloride in 2.35 mole of redistilled pyridine. The data after recrystallization twice from 90% ethanol, is given in Table I.

V.p-Lauroa:y cinnamic acid (p-dodecoyl cinnamic acid) 0.22 mole of p-hydroxycinnamic acid was reacted-with 0.44 mole of lauric acid chloride in 2.35 mole of redistilled pyridine. The data after recrystallization four times from a 1:1 benzene-- methanol mixture is given in Table I but it may be added that the compound was found to sinter at 135 C. prior to forming the turbid liquid at 159-160 C.

VI.p-Palmitoxy cinnamie acid (p-hezcadecoylorcy cinnamic acid) 0.3 mole of p-hydroxycinnamic acid and 0.6 mole of palmitic acid chloride were reacted in 3.3 mole of redistilled pyridine under conditions as set forth above. The data on the compound after recrystallization from a 3:1 benzene-methanol mixture, is given in Table I but it may be noted that the compound was found to sinter at 139 C.

In these various examples, the proportions may vary but to avoid by-products as far as possible, the mole ratios as given are best employed.

As noted, the p-acyloxycinnamic acids beginning with the butyroxy derivative show the property of forming liquid crystals on melting and the length of alkyl or analogous substituent I active decarboxylation group may be selected to give this property. While several by-products produced by esterification of a p-acyloxycinnamic acid with phydroxycinnamic acid have been noted, any of the entire series of such esters may be produced including those formed with any of the particular p-acyloxycinnamic acid as set forth below.

Such by-products may be obtained, as for exam-' ple, in the production of p-butyroxy and 13- caproxy cinnamic acids, by slowly cooling the solution of acids in alcohol. Analyses of these high melting by-productsindicate their structure, as in the case of the specific by-products men-- tioned, to be OH=OHCOOH in their decarboxylation to form corresponding p-acyloxystyrenes that are of particular value for the production of polymers both homopclymers and copolymers. So that monomeric p-acyloxystyrenes are valuable products and may be readily produced in accordance with the present invention. Decarboxylation may be carried out in a variety of ways to produce substantial yields of the desired product. The desired p-acyloxy cinnamic acid may be heated to decarboxylatmg temperature desirably in the presence of a polymerization inhibitor, and desirably in the presence of a solvent. Any of the p-acyloxycinnamic acid derivatives referred to above may be subjected to decarboxylation to split off CO2 and, convert the corresponding CI-I=CHCOOH group to -CI-I=CH2.

While decarboxylation may be carried out by or by dry distillation of the acid with soda lime, the more desirable methods include decarboxylation by heat in the presence of quinoline and copper powder desirably with an added polymerization inhibitor. Decarboxylation may be carried out in some instances at least inthe absence of the copper, the quinoline itself acting as a catalyst, or decarboxylation with copper'alone.

salt of the I as zinc or iron; or decarboxylation may also be effected by the use of mineral or organic acids. v

Any desired polymerization inhibitor for the styrene derivative may be employed such as p-tert. butyl catechol, picric acid, hydroquinone, m-phenylene diamine, nitrobenzene, phenol, sulphur, phenyl-B-naphthylamine, trinitrobenzene, resorcinol, etc. It may be noted that the copper itself acts to inhibit polymerization but other added inhibitors may be used. The picric acidif used, imparts a yellow color to the distilled product but does not change its refractive index. In some cases, as in p-capryloxystyrene, some solid distillate may be recovered also.

The decarboxylation reaction is fairly rapid and may for example, in the case of the preferred procedure, be completed in less than an hour, i. e. forty minutes. Decarboxylation usually begins around C. after which the temperature may be maintained between that of and the boiling point of any solvent present, such as quinoline. Active gas to bubble through lime deearbexv atio is vi enced be ween ;.1 .,.an.d 80 'C- with max m m rate in eneral. around 2Q 21 C.

- he ll inesen r pro ed e maybe u z desirab or d e rb xv at on- Und r an at sp er f ni ro n. de irab ,0 par i pa by wei ht un ess o herw s i l ated) of t e meadow i n m c ac 39 parts o ui oline. an a small ame nt .o p-te t. ut l cateeh l r a ded n d st n flask. a dhee ed by eans 0i an oil bath. Wh n t e acid h d disso ved i the-.quin li -0 coppe pewr was int o u ed and t e em er inc ea at a moderate rate until (around 1.40? C.) d?- carboxylation of the acid began. The evolving carbon dioxide may be detected by allowing the water. Y At this point the temperature was increased slowly until the vapor temperature reached the boiling point of quinoline (235 0.). The period of decarboxylation was generally about 40 minutes. The purification for each styrene-may be varied, but the following general procedure may be noted.

Distil the contents of the flashat reduced pres sure in an atmosphere 'of nitrogen. The distillate is taken up in ethenwashed several times with 2.4 N hydrochloric acid, followed by aqueous sodium bicarbonate washes and water washes and addition of anhydrous magnesium sulfate. To the ether extract, a small amount of p-tert. butyl catechol is added and the ether removed by distillation. The remaining liquid is distilled at reduced pressure in an atmosphere of nitrogen. A colorless liquid is obtained which is further purifled, if desired, by one or more fractionations. The general procedure outlined above was followed in all the examples set forth below unless otherwise indicated. The proportions as given in the above example may be varied but are desirab y mp oyed.

VIL-p-Vinyl phenol propzfondte After the period of decarboxylation was over, the reaction mixture in .the flask was distilled VI 12 .-p-Vinyl phenyl Zaurate After decarboxylation, the reaction mixture was distilled under reduced pressure and the distillate was dissolved in ether. The ether solution was washed thoroughly with cold 2.4 N. hydrochloric acid, dilute sodium bicarbonate solution and water. The fraction distilling between 144 and 157 C. (1 mm.) appeared to be solid at room temperature, so the purification was carried out by recrystallization from 95% methanol. After recrystallization four times, the compound decolorized bromine in carbon tetrachloride solution readily, and melted at 44-45" C. The datais given in Table II below.

The impurities, separatedfrom the recrystallir zation, melted difiusively at about 95 0. Analysis showed that the composition of this material (C, 79.09; H, 10.65) was close to that of the monomeric p-vinyl phenyl laurate, but the compound did not take up bromine readily. The material was believed to be a polymer of the substituted styrene.

The reaction mixture, after clecarboxylation, was separated fromthe copper powder by filtration. The filtrate was mixed with ether, and the ether solution was washed thoroughly with cold 2.4 N. hydrochloric acid, dilute sodium bicarbonate solution and then water. The crude yield, after the ether was removed by distillation, was 90%. It is believed that some palmitic acid might be mixed with the crude product. The crude product was recrystallized three times from 95% methanol. The compound readily decolorized bromine in carbon tetrachloride solution. The data is given in Table II.

These examples illustrate methods of decarboxylation and the table below gives data in this connection as well as with respect to other pacyloxystyrenes.

TABLE II.P-ACYLOXYSTYRENE Molecular PercentHy- Yield Refraction Pemgnt Carbon drogen R e. 1 O 0. (mm) -fi me am a Formula 4 g Calcd. Found Calcd Found Ualcd. Found 0113.." 80 '37 1.,5397 l. 0548 lfi. 28' 48.22 010151092- 74*. 05 73. 79 5. 98 5. 98 Or an- 85-865 (1) l 5O 1. 5303 l. 0402 50. 88 52. 011111102 74 99 74. 62 6. 87 6. 88 11-03317. 95"96 (2) Z 34 1 5238 l. 0156 55. 57'. 3O ClsHilOz 75. 76 75. 03 7. 42 7. 4]. 11-0511 112-113 (1.5) l. z 43 1. 5145 O. 9880 64. G9 66. 014E150! 77. 03 76. 86 8. 31 8.41- D-C'IH 5 129-130 (2.0) 2 31 1. 5074 0. 9670 73. 9Q 75. 84 015112202 78. 01 77. $7 9. 00 9. 12 D-CnHga M. P., 4 5 .0. 77 20113002. 7 42 79. 45 10. 0D 9. 99 n-C 15Ha 1 59-60. 7o CgaHiisOj 80.39 80. 2a 10. as 10.79

The styrene derivatives mentioned in thispaper exhibit optical exalation as expected, since a conjugated system is present, partly within the ring. and partly within the side chain. In addition,. as for any homologous series of compounds, the exaltation is constant within an experimental range of. error. The increment R011 evaluated-.irom the experimental ,rnolar refractions, varies from 4.52 to 4.62compared to the given value, 5.6, for liquids at 2'0 and the D line. The calculated andexperimental values for the; compounds prepared anddescribed here are listedin Table II.

The monomers produced in accordance with the present invention contain straight chain alkyl groups which when polymerized give a polymer with this alkyl group in the side chain. In particular the formation of crystallites in such a side chain and the influence of this crystallization on the polymer or copolymer properties are of special interest as for example in chewing gum base compositions.-

Having thus set forth my invention, I claim:

1. The method of preparing p-acyloxystyrenes which comprises acylating p-hydroxycinnamic acid to form a p-acyloxycinnamic acid and decarboxylating the latter to form a. p-acy1oxysty-,

rene, the acyl group being a fatty acid acyl of at least three carbon atoms.

2. The method of making p-acyloxystyrenes which comprises heating to de-carboxylating temperature a p-acyloxycinnamic acid in which the acyl group is fatty acid acyl of at least three carbon atoms, in the presence of a polymerization inhibitor.

3. The method of claim 2 carried out in the presence of quinoline and copper.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,276,138 Alderman et a1. Mar. 10, 1942 2,485,125 Wilkinson Oct. 18, 1949 

1. THE METHOD OF PREPARING P-ACYLOXYSTYRENES WHICH COMPRISES ACYLATING P-HYDOXYCINNAMIC ACID TO FORM A P-ACYLOXYCINNAMIC ACID AND DECARBOXYLATING THE LATTER TO FORM A P-ACYLOXYSTYRENE, THE ACYL GROUP BEING A FATTY ACID ACYL OF AT LEAST THREE CARBON ATOMS. 